Olefiwej



Patented Aug. 10, 1943 .Antonjohan.Tulleners, Long 4Beach, Calif., ras v- Msignor to" Shell Development Company, SanV 'f lranciscopCalif.,avcorporation of Delaware I @Application-:May 29,19am-semiNdzvaaitj..

f o Great Britain 'July 1,9, 1938 Y 41'Clams. (Cl.` -f

Vi lThis invention relates; to;;ther;pr0duction of alcohols ofy six or :jmorercarbonatomsv per mole- :cule which Aare;substantially.mater:insoluble It deals with a new fandmoreadvantageous method of Vproducing` suchalcohols. from.=.the corresponding olenesfand is,=..-particu1arly concernedwith 'a .the manufacture: of; secondary y alcohols from olenic hydrocarbon mixtures-by .reaction with a fstrong .acidsandfzhydrolysisz of :the resulting '-westers.

f 2 Aneimportantcobject-m ofmyvrinvention is the `provision `of af :more- 'efficient'. YandA economical fmethod for producing .higher alcohols in a pure form. --Anothenfobject is .to'ireducethe cost of vvfsuch alcohols; andsparticularlytof-reduce the consumption of l'acid' .in the 'productionof higher l secondary :alcohols 5l-Other objects.A include' the more Y'eiiicient utilization of the.- startingfmaterial and morei complete ,recovery of: the'alcoholproduced whereby higheriyields ofwdesire'd vproducts may beiobtainedatlessexpense I-t'isfa further object oflinvention-ato providea-'--simple "method- 4for-producing :secondary :alcohols of six Y or more carbonatomsfree fronifundesire'd homo- 1 log-ues -aslvvell as hydrocarbon and other f impurik-ties,from'zolefnicrmixttires.

The process of my invention may be appl-iedin lthemanufacture of secondaryand/orftertiary *alcohols of six ormoref-carbon-,atems per molecule or mixtures thereoffromthe corresponding Y- -oleiines regardless? of-=theirsource or'pleiine content. As suitablerfstarting=materialfor theifprep- 'arationoffsuch alcohols, @hydrocarbons derived from mineraloils,- as petroleum, shale oil andthe fflike; orfrommineralien-products, or-coal, peat and like carboniferousfmaterials,-may be used; as

well as derivati-vesL oft animal or vegetable oils,

" `Afats and-waxes'.f"'llieoleiines present in such "starting-material may be off-natural` occurrence, the -result of a "Tdehydrogenation, .h-distillation,` vapor or liquid-phase-'crackinglon other pyrogenetic treatment or various*combinations of such f treatments maybe used `in preparing the l{"i'nitial -oleiinic-material.t Thelolenes'may be applied in a pure lstate,-either as individual oleaction Without interfering -Witlimy process. 'l

Y -Suitable-facidsp-Which may beuse'd in fconverting higher olen'es to alcohols in accordance With i 'phosphoric; pyrophosphoric-` andthe like are typif cabane. organic acids 'such-'as benzene andnaphloguesthereof.

-thalenesulilcnic acids and 'homologuesjand ana- The concentrations, temp'eratures,proportions Oirreactants 'and timek of re- .,'action to be Vused will varyf'with the particular combinationg'of olefine and acid-chosen-.fcrjuse` e My` invention is broadlyappl-icable to the manuiacture` of alcohols' of :six or morecarbonatoms per moleculer-- from the correspondingijfolene Whether theo1ene be of straight. chaintype such as thefnormal hexylenesyheptylenes, Yvocty- 1 lenes,:` vdodecylenes,Qceteneiand the, like, Vvor Y' branched chain secondary! olenes suchVV as 2- j -methyl,-pentei'e4-,'` A2.-methylhexene-5, fthe1v2,2" dimethyl-pentenes and thellike 'or tertiaryble'- v1iines, such .as.ZTmethyl-pentenelor 2,3 m'ethyli VheXenelor 3,*2-ethyl pentene'l, 2,2,4v-tr`imethyl` pentenes and .the like or cyclic :olenes aslcyclo- A hexene, .-1methyl-cyclopentenel,-methylenecyccation to the preparationoflhighersecondary"p,

-alcoholsirom normallyV liquid olefines ,obtain-r able by suitable cracking of higher. parafnic hylohexane and the like; FrLfthe-,purpose Iof mak- 20 ing myinvention more clear vit ,Willi be described in detail with particular referenceft'o Yits applidrocarbons. These. oleines. offer particular. ad-

' vanta-ges in the 4manuiactureofhigher alcohols tbut'1t vvilll; e understoodthat my invention is not limited thereto as noty only may the same alcohols be-obtainedvfrom the same olenes from other .sources-but also V'the same principlesinayV be applied to the preparation of other alcohols from otherolenes of six orvmore carbonatoms Y -by'proper change of operating conditions Where required. In particular, where the `same or'other startingmaterial is used,Y it may be de'sirablelto i iirst apply a suitable preliminary treatment for f-selectiveremoval of certain:components` Thus',

if diol-einesfare present ythey maybe advantageously-removed by meansfof-cuprous chloride', either asjan aqueous slurryoran anhydroussuspension or vin a supported form oras an aqueous "ethanolamine or like solution. .Alternativelydi- .lute sulfuric acid and/or phosphoric acid may be used for the removal of diolenes. By proper adjustment of the acid .concentration tertiary ole-v i nesmay be separated from the secondary Qle-l fines `presentand converted to alcohols in accordl. l

i fance with my process or usedior the manufacture of'ethers Vas desCribedi-n U; S.V Patent-'1,968,1-

601 orconverted topolymers or other valuable 'derivatives or regenerated as described -in 'Y Y Patent"2,012,785 or otherwise' used;wv Suitable f tr'eatment aSWith caustic or-*le'a'd plumbite or f fthelke fortheremoval of sulfur compounds o'r 'other-impurities may alsol be ycarried `out prior vstraight chain beta olefines.

i greater esters K undesirable side reactions.

to treatment of the olefines accordance With myinvention.

'For the preparation of secondary alcohols of six or more carbon atoms per molecule, I prefrably use as starting material higher paraiinic hydrocarbons. Particularly desirable are hydroably parainic hydrocarbon mixtures Containing lessthan about 25% of oily constituents and most preferably parainwaxes having melting points 'above about 80 F. Paraiiin cakes', slop Wax,

petrolatum and the like are suitable. While any suitable method of converting suchstarting Vmaterial to oleiines of six ormore carbon atoms may avoid polymerizationy and reactions. AUnder such-preferred cracking conditions, distillates may be obtained having anoleflnic content preponderantvly composed ofj straight' chain oleflnes andV substantially devoid of branched chain yor cyclic unsaturates. Furthermore, these oleiines are predominantly lalpha oleiinfes, the remainder being A The alcohols obtainablefromthese cracking `Vdistillate's by sulfation and hydrolysis substantially.consistV of A y `straig'ht'chain secondary alcoholshaving the hydroxy group attached to the second carbon atom with a smalleralmount of the corresponding al- A v cohol having the hydroxy group attached to the third carbon atom. kThese 'alcohols providejan advantageoussourceof pure individual ketones since they Vmay be dehydrogenated in accordance with U. S. A PatentV 1,952,702 to produce inixtures of methyl and ethyl ketonves' whichmay be separated by means of the crystalline "sodium bisuli yfite addition products of the methyl ketones.

'j Inthe VKpreparation of secondary alcohols of six or more carbon atoms per Vmolecule in accorda-nce withrny invention, Iiind thatA unexpectedadvantages'may be'obtained by operating seconds and most prefer carbon mixtures rich in paraflin waxes, preferto obtain mixtures of olenes having boiling'. ranges such that the boiling points of the al-P cohols and any polymers formed therefrom differ? v sufficiently from each other and from the boil- 4 ing points of the initial olenes to enable asatisfactory separation of the resulting second- Vary alcohols to be made Yby fractional distilla-KA tion.1 Preferably alsoifractions are chosen which have such boiling ranges' thatfthe resulting' higher' alcohols can subsequently be separated in a vpure `state by means of fractional distillation. In the'preparation of higher alcohols containing upto 9 carbon atoms in the molecule this 'result may be attained by starting from a Cri-C1 f or. from a Cri-C9 cracked distillate fraction, ob` tainable by suitable fractionation of a liquid cracked-distillate containing olefines with up to 9 carbon atoms in the molecule. In case the fractionation has not been sufficiently sharp, so that a small quantity of Ca-olene is left in the Cs-Cv fraction, ythe amount of Cs-olene which is'alwayspresent in this fraction shoulcljbe -removed, since otherwise the Cs-alcoho'l formedby sulfatio'n and .hydrolysis` of the crackedfraction cannot berecovered in a pure stateowing to its boiling point lying too close 'to that of the Caolene, while moreover the C2i-alcohol would'remain contaminated with dimer of the Cs-olene. After removal of C's-olene the presence, of Csolefine in the cracked Ces-C7 fraction is. less obv jectionable.. Since the removal of Cs-olene,

however, makes. aseparate ldistillation necessary,

itis more economicalto start from a .Ca-Cv fraction which doesnot contain C-olene. Y

The Cia-C9 olefine fraction should not contain vany Cin-oleiines, since otherwisathe Ciovoleiines .present in theV ,hydrolyzed sulfation with narrow fractions consisting of individual olenesforof mixtures of olenespreferably? difj fering in carbon content by not more than one carbon atom per molecule.

Such fractionation has not previously been considered'necessary because the boiling points of the homologous secondary alcohols permit their ready separation from each other by distillation. I'ha'vefound,

however, that ypure higher alcohols may be obtained in a more simple and economical inan- ',nerthan if'the-'prior artmethodsiusing the "entire cracked distillatev are employed. Byv this feature of my invention notdonly is theV use of Vv'complicated installations, particularly those .re-

duired for recovery of product from lpolymer and other undesired lby-pro'd'ucts 'avoided but also In' orderto-make this feature of my invention clear it will be'described in more detail in lconnection with 'the` preparation .of secondary alcohols 'containing' six to nine carbon atoms in the molecule, in which application it is especially advantageous. VAs thus applied,'the cracked distillate is preferablyclosely fractlonated'so as product could not be separated from the Cs-alcohol,Preferably noLC'r-olefine should be Ipresent in this'fraction either, the separation of -Cialcohol Ifrom Ce-oleiihe, though-feasible,y being Vrather diiiicult.l The Csand Cn-alcoholsformed by hydrolysisof the sulfated Ca-Cg olefine fraction can readily beseparatedfin a pure state by i' fractional distillation from the non-converted Ca and Cg-olenes and the polymers of l these olefines.

Whether or not'this advantageous feature of my invention,..namely treatment of Vfractions containing olenes differing in chain length by not morelthanone carbon atom per molecule, is used, the conditions ofreactonfof the olenes with acid should be chosen with due regard for the natureof the, acid and-,oleiine or oleiines involved For example, in :the sulfation of cracked distillate containing preponderantly straight chain alpha and beta olefines of six or more carbon` atoms,- concentrated acid, prefer- VablyY of about 85 -toff100% concentration. andv most preferably 90 to96r% sulfuric acid, may

be usedat temperatures-'ranging from about flexibility Y`'of' operationY is achieved. for example., the formationv of neutral 10 to-v about 40,"v C., preferably about 0"y to Y"-eC'.. The higher ythe -acid concentraf tion used the lower the temperatures preferably employed. Too high',A temperatures Vand acid concentrations, may y,cause undesirable polymerization vor Ydecomposition of sulfationl products or both. For a .givenV acidA concentration the temperature in, general is preferably lowered as `the;molecular weight diatheolefineV used increases.- Thus .when sulfuric. acid was yused for the-sulfationofa Cs-V'Cccracked wax-fractionthe best `results wereV obtained at Al5 toz2`0 7 .C. In sulfatingnthe corresponding C10-,C12 fractiona temperature, ofaboutf 15 is preferable from. 7' Iv have fur procedure fof-fthe- :malufa'cilure A"of 'secondary 'lfated: and fthe'` 'resilitingV ikiyr siiif'ates Techy-50 .drolyzedunder isuehicof-i tiene of Yacid'l 'concentration that the-iowerulayeroistiriable by kStati Y preferred'v range;

slow even' when high-1"temperaturesfoie*used. When the dilution is such that'ani'c'id o'f'io're which' give practicallhydrlysismies. Y "Noffohly is the alcohol yield "thus reduced-'but 'also-"thel'" l pmity of the alcoholsformed lis maeriaglly lwf Y Content of aikyi:suifatesiof-"me femdom-mixture51%@diede-gewaden' .intoE fwd lzveirsjmiylqtipcpur *the essential 15d-.my inventief: in

until after theaddition ,of a ,demulsifying agent, e, g..ethanol, acetone or the like-,the sulfation product otherwise remaining `in theiiform of a non-readily. separatableA emulsion, owingY to .the

strongly emulsifying ,properties of the highervacid I alkyl sulfates. VThe temperature vduring. vthe separation into two layers should be low-preferably below 25" C. since otherwise `hydrolysis may already occur to a certain extent, which is not desirable in this stage. Y.

'Besides mono-alkyl sulfates l maining after removal of the polymerV layer the lower. layer reu'sually still contains a certain amount of poly- Y mers, non-converted cracked distillate -and'jdialkyl sulfates, the separation never being quanti- Part o f these .impurities can boiling points corresponding to those of the alcohols cannot be` separated from the alcohols by j distillation and alcohols obtained 'in thismanner in `general have` `a purity not exceeding Ivabout I have found that substantiauy pure, alcohols l can be produced by subjecting thev sulfated mixture, after the second dilution according Vto the invention and prior to the'hydrolysis, to-an ex traction treatment with a hydrocarbon or hydrocarbon mixturee. g. pentane, benzene, gasoline and the like, which has a boiling point or boilingVV hol or alcohols to be produced, to permit Vsepa-5. `ration of the extractant by distillation. Iprefer toV use hydrocarbon solvents boiling below. theV boiling point of the lowest lboiling alcoholbeing manufactured. It isof advantage first to separate thediluted sulfated mixture into two layers tor not puried inany or al1 of the foregoing ways,

is preferablycarried out under conditions promoting intimate contact of the two liquid phases Y presentduring hydrolysis.

f cause otherwise the higher alcohols formed dur- This is desirable being hydrolysis form a separate layer from the hydrolyze more slowlyand so prolong the time of treatmentnecessary and increase the size of equipment required. I therefore prefer to carry l out the hydrolysis in apparatus provided with an eiective mixing device. Suitable stirring devices or a pump adapted for recycling the mixture under treatment or other means of maintaining the alcoholphase in intimate contact with the acid may be used. Under such conditions substantially complete 'hydrolysis-may, be attained in 4 to 5 hours even where large amounts of di-alkyl sul- -.iates are present. l

The hydrolysis may be carried out under normal orsuperatmospheric or reduced pressure and iperatures of about 85 to 110- C. are generally mostV convenient. The hydrolysismay-.be conducted under conditions at which one or more 1 y "components ofthe mixture distill. Thus, at 100 range suiiiciently different from that of the-alco-A C for example, the extracting agent may be dis- -tilled :oi completely. Any-de-emulsifying agent alcohols being producedmay be distilledeither and apply the extraction treatment to the result- .i

inglower layer, after removal of the upper polymer layer, the quantity of material to be extracted beingv thus reduced. V The extraction is preferably; carried rings or the like.

ethanol, -is preferably added in orderto prevent the 'formationof emulsions during the extraction.A

The extract phase obtainedcontains the greater part of the extractingagent, substantiallyall the di-alkyl sulfates, polymers yand non-converted initialmaterial, andfurther a slight amount of ent-rained free sulfuric acid andfmonoalkyl `sulsimultaneously with or subsequently to thefremoval of lowerboiling components.

Y e Especially in thecase-of mixturesyielding alf cohols of six to twelve-carbon atoms, it may be advantageous to carry out the Yhydrolysis in such a manner that all the alcohol or alcohols of such type aredistilled oi during the process. In such a case it is desirable to cool the distillate partially,.for example, to 90to 95 C'. and to return the vv.lower-aqueous layer formed on stratiiication'of the distillate to the hydrolyzing apparatus, whereby substantial heat economy is effected and y the acid resulting from the hydrolysis is prevented from becoming too concentrated.

In general it is, however, more economical and thus preferable-to carry out the hydrolysis while ing agent, water and possibly also ethanol or anlate, l which acid compounds @can easily beremoved by washing the extract with water, vpreferably the water-whichV is toloe usedfor the dilution of the sulfatedv mixture. Incase a preliminary separationof the polymer layer has been effected, this layer may be combined vwiththe extract, whereupon the resulting mixture may be washed for the .removal ofvfree sulfuric acidand monoalkyl sulfate and worked up further as will be described below. Y

The raffinate phase contains `the mono-alkyl sulfates, free sulfuric acid, water, ethanol or an-f other demulsiying agent if such agent has been employed during the extraction, part of the extracting-agent and-traces of polymers and non- `converted initialmaterial.

other deinulsifying agent used in the extraction treatment, is then cooled, as a result of which .it separates into two layers, an upper layer containing thehigher alcohols and the extracting agent anda lower layer containing water and The upper layer may-then, after a simple neutralization with soda or diluted ,caustic alkali be 'fractionally distilled for separating and recovering the extracting agent and, if desired, separation of the higher alcohols into fractions.

After completion of the hydrolysis the higher alcohols vwhich have not distilled overV may be Y separated. as a top layer fromthe acid resulting from the'v hydrolysis; this acid practically does ynot contain any organic matter or inorganic salts and can readily beV reconcentrated.

Owing to the `presence of small amounts of sulfonic acids and other organic sulfur compounds these non-distilled alcohols are preferably not distilled as such, or even after a simple; neutralization treatment because these sulfur compounds Y innocuous by treatment in accordance with U. S.

Patent 2,139,179; For example, the crude alcohols Vmay be treated at elevatedY temperatures, e. g. at about 100 C., with a solution of caustic alkali having a concentration of or more. After this treatment, whereby the sulfonic acids and othersulfur compounds are saponied and` converted into neutralcompounds which for the greater part remain dissolved in the higher alcohols, the alcohols can be distilled without any risk of losses owing toV condensation or other undesirable side reactions. After the caustic alkali lye has settled and been brought again to the required concentration, it may be reused for the treatment of further crude alcohols.

The higher alcoholslobtained inthis manner,

have a purity of 97 to 100%. Y

The extracting agent present in the extract phase can be recovered, ltogether with any alcohol or other demulsifying agent that mayk be present, by distillation., VDuring this distillation the di-alkyl sulfates-are decomposed into sulfuric acid, alcohols, oleiines and polymerization products thereof, and from the product thus remaining after the recovery of the extracting agent the alcohols cannot readily be recovered. The olenes formed may be returned to the` sulfuric acid treatment stage of the process. Y

Now it has further been found 4that thejdialkyl sulfates present inthe extractphase and/ orkv the separated polymer layer can economically be subjected to a saponification treatment. This saponication, which is carried out by heating the extract phase or the polymer layer, or the extract phase together with the polymer .layer,re. g. to a temperature of 100 C., with an aqueous or alcoholic solution or suspension of an inorganic or organic basic compound, such as sodium,- potassium, ammonium or calcium hydroxide, triethanolamine, ethylenediamine, triglycerylamine, sodium or potassium'carbonate or the like, results in each molecule of di-alkyl sulfate vbeing converted into one molecule of the'corresponding salt of the mono-alkylsulfate and one molecule of higher alcohol.` ,If the saponication is effected by means of an aqueous solution or suspension, it is advantageous tostart the treatment in the vpresence of a sufcient amount of the estersalt to be formed, to produce a good emulsion in the mixture. The saponication proceeds readily under such conditions while sucient ester salt is formedto'maintain this emulsion during ythe remaining part of the reaction. f A

DuringA the saponication all the extracting agent (and alcohol or other `Ademulsifying agent, if present) may bedistilledover, togetherl with a certainr-amount of. water, which is preferably and polymers may Valso be distilled over. Y

The vsaponiiied reaction mixture- -containin alkyl estersalts,l non-convertedcracked distil`` late, polymers and higher alcoholsgwater and a` small excess of the base ,used inthe saponicaf tion, is then freedfrom kthe oily constituents. ,To this' endthe mixture isv first diluted withwater until the alkyl ester ksalt concentrationY is about 15%, if .necessarywhile adding ethyl alcohol ,orf another demulsifying; agent.l The diluted 'mix-lv4 'l Y ture may be stratified and the polymerY layer con- 7 taining tlieugreater part o`, .l he non-converted cracked distillate, thepolymers and the higher' alcohols preferablyl separated. The 'diluted rnix-Y ture or the lower layer thereof remaining after? removal of the polymerylayer 'is subjectedtooafcountercurrent extraction treatment .Withg a suitable extracting agent forthe'hydrocarbons and g alcohols ;still present. Suitable extracting agents 1 are,` for example, 1 gasoline, jpentane, y benzene and the like# Wheny cracked distillate'boilin'g fromll w Y to ,160 C. is taken'as starting materiaLgasoline boiling from to 100C.1is very suitable asextractingagent, while with' cracked Ydistillate, boiling above' 160 C. one may advantageouslyuse gasoline boiling from 80 agent.

The Vraiiinate phaseobtained by the extraction ofthe; alkyl ester salt solution, consists'of an 'f aqueous solution vof alkylV ester salts containing slight; amountsY of extractingagent'andf is practically devoid of inorganic salts.` /It is, therefore, ;V very suitable for the preparation of alkyl ester' salts -withv a very lowcontentofj inorganic `salts, Y to which end the solutionis evaporated ,for the recovery of the extracting agent presenttherein,

whereupon the ,resulting concentrated aqueous Y alkyl estersaltsolutionjs eitherfused assuchorv Y converted to powder byv drying and pulverization.

Instead of being Worked upto alkylester salts the raflinate phase may also be used for the pro-y duction of higher alcohols by acid hydrolysis. V'I lhe acid to be added for effecting this hydrolysis may..v be part-of the acid initially separated olf fromethe Thev amount of lacid should sulfation mixture. be so adjusted that the concentrationof the acid after the hydrolysis lies inthe same ranges as' I that of the acid afterthe hydrolysis of the mono-f... alkyl Vsulfate-containing layer. -Theg hydrolysis and the treatment with causticalkalilye of any non-distilled alcohols is advantageouslyfcarried out in the samemanner as that of the lmono-l alkyl sulfate-containinglayer.`

Alternatively thegrefined alkylrsulfate Y salt sphition may also lbe combined with the Vrenedacid, alkyl sulfate solution, whereupon` the resulting,

mixture may beV lsubjected to vhydrolysis without any special addition of acid andfurther worked t up to alcohols in the saine'fmanner as described with respect tothe separateltreatrnent of there@ fined acid alkyl'sulfateV solution. When the mixev ture has been Lthus treated, thejacidresulting from-the hydrolysis contains sodium bisulfate or other sulfuric acid salts Awhich may interfere with reuse and/orY reconcentration of Ythe acid.

If it is desired ftoreconcentrate thefacid under such circumstances, the hydrlysis of the acid alkyl sulfate solutionV (which yields acid free from sodium bisulfate or-'oth'er salt fandV can; readily `A be reconcentrated) should be kept separate fromVV the hydrolysis of the alkyl sulfate salt solution". if

If carried out separately, the higher alcoholidis#Y ,I tillates and .the crude alcohols, 'after treatmentV to C.j as `extracting z with lye, obtained inthetwo hydrolyzing steps may be combined andthe-pure alcohols recovered therefrom by fractionation.

The' extract phase` obtained inthe extraction of the alkyl sulfate solution, together Vwith polymer layer which may be separated prior to` the extraction, is preferably Washed with water in order torem'ove any alkyl sulfate -saltl which may The-resulting extract is preferably: usedfor dilution vof the alkyl sulfate salt solution.:

be present.

The WashedY mixture isi combined with the distillate obtained during` the lsaponication of the extract'from the acid alkylsulfate solution and subjected to fractional distillation, whereby a distillate is obtained consisting of theextracting agent used, together with any components of Y the non-converted cracked material thathave .the sameboiling point orrange.' y i vThe distillation residue, consisting of non-con-v verted cracked material, polymers and higher alcohols, may be separated by fractionationinto bottoms consisting of the polymers and a distillate lcontaining the noneconverted crackedmaterial (comprising oleiines and parafiins) and the higher alcohols resulting from the saponcation ofthe di-alkyl sulfates. This distillate, the so-called polymer distillate, isquite suitablefor being subjected to a renewed sulfation, preferably Y by means of acid of higher concentration, ve. g. 96% H2SO4`, thanv in the first sulfation treatment.

The resulting sulfation product can then bef Worked up to higher alcohols or to alkyl sulfate saltsa f The higher 'alcohols may rst be separated from .the hydrocarbons by extraction'with diluted 'sulfuric acid, preferably acid of 60 t070% concentration. The higher alcohols maybe subLr sequently recovered from the alcohol-containing acid extract obtained', by extraction Vwith a suitable hydrocarbon solvent, e.g. benzene, andthe solvent removed from the alcohol extract by fractionatiom f v The extract phase, obtainedby extractionof` the sulfation product after the so-calledsecond dilution according to the invention,` preferably worked upr in the following manner. f

Sulfuric acid is added to the extractY phase con taining polymers,non-converted cracked. distillate, and di-alkyl sulfates dissolved in extracting after removal of the polymer layer, mayalso -be agent, and the mixture Vissubjected to hydrolysis while distilling off the extracting agent. After the hydrolysis the'acid-is separated off as-lower layer, the' upper layer, containing higher alco-v hols, polymers and non-convertedA cracked dis-Y in acid sulfates. Instead of sulfating the upper.V layerv from the hydrolysis alone, previously' separated polymer layer may be admixed therewith before such sulfation treatment.Y It is advan? tageous to use acid recovered in the rst dilution fory effecting the initial hydrolysis according toV this-modification of the invention'.

The product of thewrenewedrsulfation maybe worked up further in a manner analogous to that applied in the sulfation of the original cracked distillate, with the exception that, the polymer layer separated after dilution of the product of the renewed sulfati'ony and the extract need not befwo'rkedvup further as they contain practically no dialkyl-sulfates.

The following example illustrates 'one' method of applying my inventionto the manufacture'fof 1 Cei-C9 alcohols as a continuousY process. The in- Vvention may also be applied mittent operations. z:

Into an iron"reaction'vessel'fth'ereis continuezr ously introduced `a*Cla-C9cracked wax distillatel tained byrfractionation-ofa vvapor phase crack-v l ing product of aparaflinous-hydrocarbon mat..- rial and having an oleiiniccontent.composed al most exclusively of straight chain' alpha and beta mono-olens), and sulfuric acid of concentration. Using a hydrocarbon feed rate of 30 kgs.

per hour the acid vispreferablyilfedat afrate of about 30.2 kgs. perh'our. The temperature isf preferably maintainedatlab'out l5`v C. by cooling,

eyg. by evaporation fof liquefied gaseous hydro#4 carbon in accordanoeiwith 'U-S. Patent 1,055,873.`

able. Y' The sulfationfproduct is continuouslyre-V moved at a rate of Tabout 6i2rkgs. per hour and introduced into-a lead-lined vvessel in which it is diluated with 'Water addedfat a rate of 9 kgs. per hour, the temperaturebeingkept atabout 15 C.V rfhe diluted mixtureris'fseparated lintc two layers` andthe bottom' layer,y consisting1of-60%i sulfuricacid, withdrawnat'arate of 175.2 kgs. perlhour. The top layer containing '-themono and'd-i-alkyl sulfates, non-convertedfcrackeddistillate,- poly# mersfand some-*free sulfuric' acidfisY ledlat alrate ofabout 52 kgs. per hour-*to a lead-linedvessel I .in which a'second dilution-is'carriedfout by mix'- ing water introduced'att a rate of 560 Vkgs.`

per hour wherebyianlaci'd concentration'cf about ratorin which '-anupperl polymer layerlis f allowed v to separate;v This'layer'iswithdrawnwhile theflower 'impur-ef alkylsulfate" lay'r is extracted-fincountercurrent A'at2'0 G.`-vilith'50%V byI volume-off sulfates-,- non-converted: cracked? distillate' and-1 polymers in gasoline,1i'5-re'moved atlv arate'ofl about 54:? kgs'.- perlio'ur and-conducted, together# with the polymer' layer le'avig-'thes'eparatcr tor a saponificationyessel Y Ihe raffinate containing about 23'.`6%`Yb'y-wt'.

of ridono-alkyl; sulfate'sj some1-gasoline andfree sulfuric acid,` isv hydrolyzedbySheatingfa-t atem-fr` perature of about10090.while-thoroughly stirring; During? th'e hydrolysis! the gasoline, t`ogether withwater andipartl 'of the higher alco-I hols formededistils'fover.

of the condensatev is removed andtliel upper 'layer f The lower water layer.

tralization vessel' at a'- rat'e'of about-13" kgs'. per.. hour. The undistilled reaction mixturef is` separated into an alcohollayenzwhichiis' removed at a ratev of. about 7.51kgs` perY hourfland" af; lower layer consisting o f sulfu'ri'ciacid of aboutfZS/b f concentration!discharged; 1-V Y The combined polymer ylayer and extract. aref saponiiied` Whilel vigorously stirring with' a' 20%- solution of caustic so'da introduced at a .rate` of 3.15 kgs. per hour. The reaction time'at about C. is about 4 hours. During thes'aponii-l cation the` gasoline, together.' with part ofv th'e non-conyerted cracked` productr and Vpolymers;

water, isvapori'zed. Thevapor mixture is.; con- .to"batch or interderisedand'separated into" alovvervvater 'layergf' which is recycled to the1 saponification and an upper layer consisting Yofl a gasoline solution of higher alcohols, non-convertedfcracked 'productv andpolymers, which is drawn off. The saponiiicationproduct, Which'contains about 25.7% Vof* sodium'V alkyl vs'ulfateland 54.9% of non-converted cracked distillate and polymers, uis Withdrawn at a rate of about 13.1 kgs. per hourzand diluted with Water fed at a rate oflS kgs. vper hour. n The` diluted sodium alkyl sulfatesolution afterpoly-- mer separation issubjectedto a countercurrent extraction with `gasolinefedat a rate .of about` ,f

10.8 kgs. per hour.

The extract phaseriscombined with the previously separated polymer lay-V .j

erand the upper layer of the distillate'frcmthe saponification. TheV resulting mixture is sepa rated by distillation vinto gasoline as top` prod.- 1 uctand abottom'produceremoved at a rateof.;l

about 13.3 kgs. per hour and'consistingqof a TESTS,

mixture of about 14% by Weight of higher alco- ,'20 hols and abo-ut 86% by'vveight of'non-converted f cracked productboiling about 100 C. and polyv c This mixture'isrtreated with 96%-,fj1zSOi to eect renewed sulfationandthe product di-j luted and extracted in the same Way as the origi- Y nal sulfation product.* Thealkyl sulfates thus obtained may be hydrolyzed Yalong with the original'mono-alkyl sulfatos.

The refined aqueous solution containing about 13.5% by Weight of sodium alkyl sulfaterand also some gasoline is fed at a rate of about 25 kgs. per

hour to a hydrolyzer with sulfuric acid of aboutl 60% concentration added at a rate of about 5 kgs. per hour. that recovered from the original sulfaticn product.

`and some Water. This vaporized mixture is condensed and stratied. The upper layer of gasoline and higher alcohols is caustic soda treated,

This acid is preferably a part Vof During the hydrolysis, which is carried out at about 100 C. the gasoline present is vaporized together with part of the higheralcohols formed` together With the'mixture of gasoline and higher alcohols from hydrolyzer distillate.

The undistilled hydrolyzed mixture is separated into an upper layer of higher alcohols,

which is Withdrawn at a rate of about 1.25 kgs..

per hour and neutralized and a lower layer consisting of acid containing sodium n bisulfate. The combined crude higher alcohols are heated to about 100 C. with caustic'soda of about 20% Y concentration While stirring, the reaction time being about one hour. The product is continu'-v ously drawn off into ya stratifier from which alcohol layer is withdrawn at a rate of aboutA 8.8 kgsfper hour and fed, together with the previously described neutralized gasolineealcohol mixture, to a fractionation column. AIn this column the gasoline is recovered as top product While the higher alcohols are Withdrawn as bottom product at a rate of about 16.5 kgsper hour. These alcohols are a mixture of Ce-CQ alcohols having a purity of about 97% and represent substantially complete conversion of the initially formed alkyl sulfates.

While I have emphasized the manufacture .of higher alcohols because'of the many advantages which my invention offers over'prior methods of producing alcohols it will be understood that my process may be applied to the production of fate salt therefrom and reacting saidv alkyl sul-v other olefine hydration products by suitable j modification of operating conditions.

ample, ethers may be produced carrying out the i hydrolysisy under more strongly acid conditions.

Other features of my invention such, for example,

as the Vdescribed 1 renewed sulfatio'n procedures f .carried out With stronger` acid after hydrolysis' off;

` polyalkylf esters,i are advantageous 4regardless of f 31 the oleiine Yderivative :being: produced and may i also Lbe used inLthermanufacture ofesters, ester salts and the like. Still other` 'variations may be; made in the described process Without Vdepartingf from my invention which is not'limited' by any theory proposed in explanation l Vvof the ,Lmorejf advantageous results v'attained fbut only` by th appended claimswherein it isfintendedjto cla sibl'einl '.vievv of thenprior art; AI claim as my invention:y Y

alkyl acid sulfate anddialkylisulfate; Withdrawing the free suiituic acid phase and further dilutingY the` phase containing the alkyl acid sulfate at about the Vsaine,temperature With l sufficient Water to produce an aqueous layer which contains after hydrolysis of the alkyl acid sulfate and stratification sulfuric acid ofrlO to 40% concentration,reinoving dialkyl sulfate from Y the diluted mixture, treating the separated dlllsylV sulfate With a base to produce .the corresponding secondary alcohol and alkylv acid sulfateV salti therefrom and Vreacting .said Valkyl sulfate saltV with the free sulfuric acid separated rfrom the sulfation product to producev additional alcohol.

2. In aprocess of producing a secondary alcohol of at least ten carbon atoms per molecule from the corresponding olonne by treating said olene with atleast an equal molecular amountv of to 100% sulfuric acid under sulfating condifv Y tions andl hydrolyzing alkyl sulfates thereby formed, the improvement which comprises dilute` Y i ing the .mixture of alkyl acid*V sulfate, dialkyl sulfate and free sulfuric acid resulting from said sulfation with water at about 15 C.`to'cause separation of a phase substantially free from alkyl acid sulfates and containing sulfuric acid of to about 60% concentrationfrom a phase containing said alkyl acid sulfate and dialkyl sulfate, withdrawing the free sulfuricacid phase l1 and further diluting the phase containing the alkyl sulfates at about the same temperature with suflicient Water to produce an aqueous layer iWhich contains after hydrolysis ofthe alkyl acidi..A Y i sulphate and stratication sulfuricacid' of10 to' 40% concentration, extracting dialkyl sulfate from the diluted mixture with a Yhydrocarbong boiling at a lower temperature than the alcoholj Corresponding to said diaikyi'suifate, treating the dialkyl sulfate with a base to produce the corresponding secondary alcohol and alkyl'sulfate sait withI the free y"sulfuric acid separated from the'sulfation product vto produceadditional alcohol.

3. In a process of producinga secondaryjalcohol often to twenty carbon atoms permolecule.-

from the corresponding olerlne by treating said l j ally novelty inherent therein-ras;broadlywas,pos.. Y

l. 1n aprocess of producing a secondary-alcohol olene with at least an Vequalmolecular amount of 80 to l100% sulfuric acid under sulfatlng con.

ditions and hydrolyzingy alkylv sulfates thereby formed; the improvement which comprises dilute ing the mixtureof alkyl' acid sulfate, dialkyl sulfate and Vfree sulfuric acid resulting from said sulfation withwater .at :about 15` C. to cause separation of phase' substantially freeA from alkyl acid sulfates andcOntaining sulfuric acid of 50% to about 60% concentration from a phase containingsaid alkyl acid. sulfate and dialkyl lsulfate,.withdrawing theffreeV sulfuric acid phase Y and further diluting the `phase containingy the alkyl acid sulfate at about .the same temperature with suflicient water to produce an aqueous layer which contains after hydrolysis of the alkyl acid sulfate' and stratification sulfuric acid ofV 10 tor 4.40% concentratiomadding a deemulsifying agent to the diluted mixture and stratifying to separate a phase containing dialkyl sulfate from a phase containingalkyl acid sulfate, treating. the separated dialkyl sulfate with a base to produce `the corresponding. secondary alcohol and alkylacid.

sulfate salt therefrom and reacting said alkyl sulfate salt with the free sulfuric acid 'separated from the sulfation productito produce additional alcohol.

4. In a process of producing a secondaryalcohol of at least. slxcarbon atoms permolecule from the:.corresponding olene by treating said oleneawith at least an equal molecular amount of.80 to 100%' sulfuric acid under sulfating conditons and` hydrolyzing alkyl sulfates .thereby formed, the improvementwhich' comprises diluting the mixture of alkyl acid sulfate, dialkyl. sulfate and free sulfuric acid resulting from said Y alkyl acid sulfate at about thesame temperature with sufficient water to produce an aqueous layer which contains after hydrolysis of the alkyl acid sulfaterand stratication sulfuric acid of 10 to 40%` concentration, stratifying the diluted mix- Yture to separate therefrom a phase containing dialkyl sulfate, treating the separated dialkyl sulfate with a base to produce the corresponding secondary alcohol andalkyl acid sulfate salt therefrom and reacting said alkyl sulfate salt 'with the free sulfuric acid separated from the sulfation product to produce additional alcohol.

` y ANTON-JOHAN TULLENERS. 

